Herbicidal method



United States Patent ()fiice P.

3,102,618 HERBICIDAL METHOD John P. Chupp, Kirkwood, and Angelo John Speziale, Creve Couer, Mo., assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware N Drawing. Filed Nov. 18,1969, Ser. No. 76,116 Claims. (Cl. 71--2.3)

This invention relates to methods of selectively inhibiting the germination and preemergent growth of plants, particularly grasses, in contact with soil which methods comprise treating the soil with a herbicidal, amount of an S-(N-cycloalkylcarbamoylmethyl) phosphorothioate of the structure wherein R and R" are like or unlike alkyl or alkoxyalkyl radicals containing from 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl, butyl, methoxyethyl, ethoxyethyl, methoxypropyl, etc. and the various isomeric forms thereof), wherein X is a chalkogen of atomic weight less than 40 (i.e. sulfur or oxygen, preferably sulfur), wherein R' is hydrogen or an aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms (e.g. the alkyl radicals methyl, ethyl, propyl, butyl, and the various isomeric forms thereof, the alkenyl radicals allyl, methallyl, but-2- enyl, and'the various isomeric forms thereof, and the alkynyl radicals propargyl, but-2-ynyl, but-3-ynyl, and the various isomeric forms thereof), and wherein R is a divalent alkylene radical containing from 4 to carbon atoms and having from 4 to 6 carbon atoms in a continuous chain between the valence bonds. It is preferred that R and R be straight chain alkyl radicals (i.e. ethyl and n-propyl), that R' be (CH H wherein n is an integer from 0 to 2 (which includes hydrogen, methyl and ethyl), and that R is a divalent alkylene radical containing from 4 to 6 carbon atoms and having from 4 to 5 carbon atoms in a continuous chain between the valence bonds, particularly CH CH 'CH CH CH These phosphorothioates can be prepared by reacting a salt (ire. ammonium or alkali metal such as sodium, potassium or lithium) of a phosphorothoic acid of the structure Kit P-SH

wherein R, R and X have the aforedescribed significance with a substantially equirnolecular amount of a halide of the structure 3-, l @2111 8 tented Aug. 27, 1963 eter, agitator and reflux condenser is charged approximately 20.3 parts by weight of ammonium 0,0-diethyl phosphorodithioate, approximately 15.8 parts by weight of alpha-chloro N-cyclohexyl acetamide, and approximately 80 parts by weight of acetone. While agitating the so-charged mass is heated to the reflux temperature and refluxed for 4 hours. The reaction mass is then cooled to room temperature and filtered. The filter cake is Washed with acetone, the washings combined with the originalfiltrate, and the solution then stripped of acetone under vacuum. The residue is then taken up with wherein R' and R have the aforedescribed significance and wherein D is. a halogen having an atomic number in the range of from 16 to 36 (i.e. chlorine or bromine). Where'andwhen desired an inert organic solvent such as acetone, butanone, dioxane, benzene, toluene, xylene, etc.

can be used. While a wide range of reaction tempera tures can be used provided the system is fluid (Le. a reaction temperature above the freezing point of the system up to and including the boiling point of the system) it is preferred to employ a reaction temperature in the range of from about 20 C. to about C.

Example I To a suitable reaction vessel equipped with a thermom- Employing the procedure of Example I but replacing ammonium 0,0-diethyl phosphorodi-thioate with an equimolecular amount of ammonium 0,0-di-n-propyl phosphorodithioate there is obtained 0,0-di-n-propyl S-(N- cyclohexylcarbamoylmethyl) phosphorodithioatewhich is insoluble in water.

Example III Employing the procedure of Example I but replacing alpha-chloro N-cyclohexyl acetamide with an equimolecular-amount of alpha-bromo N-ethyl, N-cyclohexyl acetamide there is obtained 0,0-diethyl S-(N-ethyl, N-cyclohexylcarbamoylmethyl) phosphorodithioate C H2O Hz which is insoluble in water.

Example I V Employing the procedure of Example I but replacing alpha-chloro N-cyclohexyl acetamide with an equimolecular amount of alpha-chloro N-allyl, N-cyclohexyl acetamide there is obtained 0,0-diethyl S-(N-allyl, N-cyclohexylcarbamoylmethyl) phosphorodithioate, which product is insoluble in water.

Example V Employing the procedure of Example I but replacing alpha-chloro N-cyclohexyl acetamide with, an equimolecular amount of alpha-chloro N-propargyl, N-cyclopentyl acetamide there is obtained0,0-diethyl S-(N-propargyl, N cyclopentylcarbamoylmethyl) phosphorodithioat which is insoluble in water.

Example VI Employing the procedure of Example I but replacing ammonium 0,0-diethyl phosphorodithioate with an equirnolecular amount of potassium 0,0-di(2-methoxyethyl) phosphorothioate there is otbained as a Water-insoluble product 0,0di(2-methoxyethyl) S-(N-cycloheXylcarbam- 'oylmethyl) phosphorothioate.

' Example VII Employing the procedure of Example I but replacing a alpha-chloro N-cyclohexyl acetamide with an equimolecular amount of alpha-chloro N-(4-methylcyclohexyl) acetamide there is obtained 0,0-diethyl S-[N-(4-methylcyclohexyl)carbamoylmethyl] phosphorodiothioate which is insoluble in water.

The herbicidal valueof the aforedescribed phosphorothioates was determined by planting in greenhouse flats seeds of several different plants each representing a principal botanical type. The flats were treated with 0,0-diethyl S-(N-cyclohexylcarbamoylmethyl) phosphorodithioate at the rate of 5 pounds per acre and the observations or results set forth below with respect to several typical botanical specimens each representing a principal type of plant.

. ARadish B-Sugar Beet C-Foxtail D--Crab grass E-Soybean FTomato Results (14 days after treating soil) ABC'DEF 0,0-diethyl S (N-cyclohexylcarbamoylmethyl) phosphorodithioate 0 0 3 From the foregoing evaluation data it is apparent that the phosphorothioates are selective and effective preemergence herbicides. Valuable selective herbicidal effects will be observed by applications of small amounts, for example, as low as one pound of active component per acre as well as high concentrations, for example 100 lbs. per acre. The selective activity on grasses is exhibited at lower rates of application, for example from 1 to lbs. per acre. For general application and herbicidal effect on both the grasses and dicotyledonous plants, it will be found necessary to use from 10 to 50 lbs. per acre.

Selective herbicidal activity with respect to several genera of grasses is illustrated by the data in the foregoing table. Other experiments run with respect to plants of-different genera, which have different metabolisms and physical characteristics indicate little or no inhibition of growth. The botanical types, or genera, of grasses which are effectively controlled by means of the phosphorothioates of this invention, embrace a large number of undesireable plants, or weeds, frequently found in vegetable crops. This invention, however is not limited to removing grasses from broad leaf plants since the selective activity will be useful in removing weeds from corn, which belongs to a different genus of grass. Many other crops and particularly the broad leaved plants are inhibited by weeds of the crab grass genera, which can be effectively controlled by the practice of this invention. In some instances there are minor herbicidal effects on dicotyledonous plants, and therefore optimum results may depend to some extent on experience with respect to the activity of the particular carbamoyl phosphorothioate on .the vegetable crop to be treated.

It will be apparent that quite different effects can be obtained by modifying the method of use. For this reason .an essential part of this invention is the formulation so as to permit a uniform predetermined application of herbicide to the surface or sub-surface of the soil or other growth media so as to produce the desired effect. By proper selection and proportioning of the various extending agents either liquid or solid formulations can be prepared, and so as to adapt the herbicide for achieving the desired result with any conventional device for treating the surface or sub-surface of the soil.

Although the phosphorothioates of this invention are useful per se in controlling the germination and preemergent growth of a wide variety of plants, it is preferable that they be supplied to the plant growing medium in a dispersed form in a suitable extending agent.

In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the phosphorothioates of this invention are dispersed, it means that the particles of the phosphorothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts.

In the instant specification and appended claims it is to be understood that the expression extending agent includes any and all of those substances in which the phosphorothioates of this invention are dispersed. It includes therefore, the solvents of a true solution, the liquid phase of suspensions, or emulsions and the solid phase of particulate solids, e.g. pellets, granules, dusts and powders.

.The exact concentration of the phosphorothioates of this invention employed in combatting or controlling noxious vegetation can vary considerably provided the required dosage (i.e. herbicidal amount) thereof is supplied to the plant growing medium. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g. powdered clay or talc) or other lowcost material available to the agriculturist at the point of use, he will have an easily prepared herbicidal spray or particulate solid. In such a concentrate composition, the phosphorothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well-known herbicidal adjuvants, such as the various surface active agents (e.g. detergents, a soap or other emulsifying or wetting agent), surface active clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.

There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the phosphorothioates of this invention. For example, isopropyl, ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F. and having a flash point above about F., particularly kerosene), mineral oils and the like.

The phosphorothioates of this invention are preferably supplied to the plant growing medium in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the phosphorothioate of this invention either per se or in the form of an organic solution thereof in water with the raid of a water-soluble surfactant. The term surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and in place of the expression emulsifying agent, to connote generically the various emulsifying agents, dispersing agents, wetting agents, and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition page 280). These surfactants include the wellknown capillary active substances which may be anionactive (or anionic), cation-active. (or cationic), or nonionizing or (non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berohs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical industries (pages 811-824) in an article entilted Synthetic Detergents by John W. Mc- Cutcheon and also in the July, August, September and October 1952 issuesof Soap and Sanitary Chemicals under the title, Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e. the anion-active, cation-active and non-ionizing capillary active substances are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the water-soluble anionic surface-active agents and the water-soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.

The phosphorothioates of this invention can be dispersed by suitable methods (e.g. tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the plant growing medium in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite, diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent claps, e.g. bentonite. These mixtures can be used for herbicidal purposes in the dry form or by. addition of water-soluble surfactants or wetting agents, the dry particulate solids can be rendered wettable by water, so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.

In all of the forms described above the dispersions can be provided ready for use in combatting noxious vegetation or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concenhate is an intimate mixture of phosphorothioate of this invention with a water-soluble surfactant which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with suflicient of the phosphorothioate of this invention to make 100 parts by Weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of noxious vegetation by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of 0,0-diethyl S-(N-cyclohexylcarbamoylrnethyl) phosphorodithioate and 5 parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.

Another useful concentrate adapted to be made into a spray for cornbatting noxious vegetation is a solution (preferably as concentrated as possible) of la phosphorothioate of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g. 0.5 to 10 percent by weight of the weight of the new herbicidal agent) of a surfactant (or emulsifying agent), which surfactant is also Watersoluble. As illustrative of such a concentrate is a solution of 0,0-di-n-propyl S-(N-cyclohexylcarbamoylmethyl) phosphorodithioate in acetone which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a water-soluble alkylaryl sulfonate anionic surfactant.

Of the surfactants aforementioned in preparing the various emulsifiable, wettable or dispersible compositions or concentrates of this invention, the anionic and nonionic surfactants are preferred. Of the anionic surfactants, the particularly preferred arethe well-known water-soluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the monohigher fatty acid esters of sorbitan containing 15 to 30 moles of ethylene oxide per'mole of sorbitan monoester of alkylphenol.

In all of the various dispersions described hereinbefore for herbicidal purposes, the active ingredient can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, (for example, nematocides, bactericides, and insecticides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other tonms of noxious life.

When operating in accordance with the present invention growth inhibiting amounts of the comopnud or a composition containing same are dispersed or distributed in any convenient fashion in soil or other growth media, for example by simple mixing with the soil, or by applying to the surface of the soil and thereafter dragging or disking the soil to the desired depth, or by injection or drilling techniques whereby the phosphoi'tothioate of this invention is deposited beneath the surface of the soil, or by employment of a liquid carrier (solvent or non-solvent) to accomplish the penetration and impregnation. The application of the spray and dust compositions to the surface of the soil may be accomplished by conventional methods, e.g. with power dusters, boom or hand Sprayers or spray clusters.

While this invention has been described with respect to certain embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit and scope thereof.

What is claimed is:

1. The method of inhibiting the germination of preernergent growth of plants which comprises treating the plant growing medium with a herbicidal amount of an S-(N-cycloall ylcarbamoylntethyl) phosphorothioate of the structure wherein R and R" are selected from the group consisting of alkyl and alkoxyalkyl radicals containing from 1 to 4 carbon atoms, wherein X is a chalkogen of atomic weight less than 40, wherein R' is selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms, and wherein R is a divalent alkylene. radical containing from 4 to 10 carbon atoms and having from 4 to 6 carbon atoms in a continuous chain between the valence bonds.

2. The method of inhibiting'the genmination and preemergent growth of plants which comprises treating the plant growing medium with a herbicidal amount of from 1 to 50 pounds per acre of an S-(N-cycloalkylcarbamoylmethyl) phosphorothioate of the structure wherein R and R" are straight chain alkyl radicals containing 2 to 3 carbon atoms, wherein the subscript n: is

an integer from 0 to 2 and wherein R is a divalent al kylene radical containing from 4 to 6 carbon atoms and having from 4 to 5 carbon atoms in a continuous chain between the valence bonds.

3. The method of selectively inhibiting the germination of grass seeds in contact with soil and the preernergent growth [thereof which comprises treating said soil with a grass growth inhibiting amount of from 1 to 10 pounds per acre of an S-(N-cyclohexylcarbamoylmethyl) phoswherein R and R" are 'straight chain alkyl radicals containing Z to 3 carbon atoms.

. v t 8 v 4. The method of claim 3 wherein the herbicidal compound is 0,0-diethyl S-(N-eyelolhexylcarbamoyimethyl) @hosphorodithioalte.

5. The method of claim 3 wherein the herbicidal compound is 0,0-di-n-propyl S-(N-cyclohexylcarbarnoylmethyl) phosphorodithioate.

References Cited in the file of this patent UNITED STATES PATENTS 2,959,610 Young et a1. NOV. 8, 1960 FOREIGN PATENTS 164,112 Sweden July 22, 1958 

1. THE METHOD OF INHIBITING THE GERMINATION OF PREEMERGENT GROWTH OF PLANS WHICH COMPRISES TREATING THE PLANT GROWING MEDIUM WITH A HERBICIDAL AMOUNT OF AN S-(N-CYCLOALKYLCARBAMOYLMETHYL) PHOSPHOROTHIOATE OF THE STRUCTURE 